Polymerizable compound, polymerizable composition, polymer, and optically anisotropic substance

ABSTRACT

The present invention relates to: a polymerizable compound represented by a formula (I); a polymerizable composition comprising the polymerizable compound and an initiator; a polymer obtained by polymerizing the polymerizable compound or the polymerizable composition; and an optically anisotropic article comprising the polymer [in the formula, Y 1  to Y 8  are a chemical single bond, —O—, —O—C(═O)—, —C(═O)—O—, or the like; G 1  and G 2  are a divalent aliphatic group having 1 to 20 carbon atoms, or the like; Z 1  and Z 2  are an alkenyl group having 2 to 10 carbon atoms, or the like; A 1  is a tetravalent aromatic group, or the like; A 2  and A 3  are a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, or the like; A 4  and A 5  are a divalent aromatic group having 4 to 30 carbon atoms, or the like; A x1  and A x2  are an organic group having 2 to 30 carbon atoms that includes an aromatic ring, or the like; A y1  and A y2  are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the like; Q 1  and Q 2  are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the like; and m and n are 0 or 1]. According to the present invention, a polymerizable compound, a polymerizable composition, and a polymer that have a practical low melting point, exhibit excellent solubility in a general-purpose solvent, can be produced at low cost, and can produce an optical film that achieves uniform conversion of polarized light over a wide wavelength band, and also provide an optically anisotropic article.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of copending application Ser. No.14/436,526, filed on Apr. 17, 2015, which was filed as PCT InternationalApplication No. PCT/JP2013/078099 on Oct. 16, 2013, which claimspriority under 35 U.S.C. §119(a) to Patent Application No. 2012-232314,filed in Japan on Oct. 19, 2012, all of which are hereby expresslyincorporated by reference into the present application.

TECHNICAL FIELD

The present invention relates to a polymerizable compound, apolymerizable composition, and a polymer that may produce an opticalfilm that achieves uniform conversion of polarized light over a widewavelength band, and also relates to an optically anisotropic article.

A flat panel display (FPD) that utilizes an optical film (e.g.,polarizer and retardation film) can achieve high-resolution display, andhas been widely used as a display device that exhibits excellentperformance.

Examples of the retardation film include a quarter-wave plate thatconverts linearly polarized light into circularly polarized light, ahalf-wave plate that changes the plane of vibration of linearlypolarized light by 90°, and the like. These retardation films canachieve accurate conversion of specific monochromatic light so that ¼λor ½λ retardation occurs.

However, known retardation films have a problem in that polarized lightthat passes through is converted into colored polarized light.Specifically, since a material that forms the retardation film haswavelength dispersion with respect to retardation, and a polarizationstate distribution corresponding to each wavelength occurs with respectto white light that includes different light beams in the visibleregion, it is impossible to achieve accurate 1/4λ or ½λ retardation overthe entire wavelength band.

In order to solve the above problem, various wideband retardation filmsthat can achieve uniform retardation for light over a wide wavelengthband (i.e., retardation films having reverse wavelength dispersion) havebeen studied (see Patent Documents 1 to 6).

It has been desired to reduce the thickness of the flat panel display asmuch as possible along with an improvement in performance and widespreaduse of mobile information terminals (e.g., mobile personal computer andmobile phone). Therefore, a reduction in thickness of the retardationfilm has also been desired.

It has been considered that it is most effective to produce aretardation film by applying a polymerizable composition that includes alow-molecular-weight polymerizable compound to a film substrate in orderto reduce the thickness of the retardation film. Variouslow-molecular-weight polymerizable compounds having excellent wavelengthdispersion, and various polymerizable compositions using suchpolymerizable compounds have been developed (see Patent Documents 7 to24).

However, the low-molecular-weight polymerizable compounds or thepolymerizable compositions disclosed in Patent Documents 7 to 24 have anumber of problems in that reverse wavelength dispersion may beinsufficient, or it may be difficult to apply the low-molecular-weightpolymerizable compounds or the polymerizable compositions to a film dueto a high melting point that is not suitable for an industrial process,or the temperature range in which liquid crystallinity is obtained maybe very narrow, or solubility in a solvent generally used for anindustrial process may be low. Moreover, since the abovelow-molecular-weight polymerizable compounds and the like aresynthesized by performing a plurality of steps using a synthesis methodthat utilizes an expensive reagent, the production cost increases.

RELATED-ART DOCUMENT Patent Document Patent Document 1: JP-A-10-68816Patent Document 2: JP-A-10-90521 Patent Document 3: JP-A-11-52131 PatentDocument 4: JP-A-2000-284126 (US20020159005A1) Patent Document 5:JP-A-2001-4837 Patent Document 6: WO2000/026705 Patent Document 7:JP-A-2002-267838 Patent Document 8: JP-A-2003-160540 (US20030102458A1)Patent Document 9: JP-A-2005-208414 Patent Document 10: JP-A-2005-208415Patent Document 11: JP-A-2005-208416 Patent Document 12:JP-A-2005-289980 (US20070176145A1) Patent Document 13: JP-A-2006-330710(US20090072194A1) Patent Document 14: JP-A-2009-179563 (US20090189120A1)Patent Document 15: JP-A-2010-31223 Patent Document 16: JP-A-2011-6360Patent Document 17: JP-A-2011-6361 Patent Document 18: JP-A-2011-42606Patent Document 19: JP-T-2010-537954 (US20100201920A1) Patent Document20: JP-T-2010-537955 (US20100301271A1) Patent Document 21: WO2006/052001(US20070298191A1)

Patent Document 22: U.S. Pat. No. 6,139,771Patent Document 23: U.S. Pat. No. 6,203,724Patent Document 24: U.S. Pat. No. 5,567,349

SUMMARY OF THE INVENTION Technical Problem

The invention was conceived in view of the above situation. An object ofthe invention is to provide a polymerizable compound, a polymerizablecomposition, and a polymer that have a practical low melting point,exhibit excellent solubility in a general-purpose solvent, can beproduced at low cost, and can produce an optical film that achievesuniform conversion of polarized light over a wide wavelength band, andalso provide an optically anisotropic article.

Solution to Problem

The inventors of the invention conducted extensive studies in order tosolve the above problem. As a result, the inventors found that anoptical film that achieves uniform conversion of polarized light over awide wavelength band, and exhibits satisfactory performance, can beproduced at low cost by utilizing an optically anisotropic articleproduced using a polymer that is obtained by polymerizing apolymerizable compound represented by the following formula (I), or apolymerizable composition that includes the polymerizable compound andan initiator. This finding has led to the completion of the invention.

Several aspects of the invention provide the following polymerizablecompound (see (1) to (9)), polymerizable composition (see (10) and(11)), polymer (see (12) and (13)), and optically anisotropic article(see (14)).

(1) A polymerizable compound represented by the following formula (I),

wherein Y¹ to Y⁸ are independently a chemical single bond, —O—, —S—,—O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—,—O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, R isa hydrogen atom or an alkyl group having 1 to 6 carbon atoms,G¹ and G² are independently a substituted or unsubstituted divalentaliphatic group having 1 to 20 carbon atoms that optionally includes—O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—,—NR²—, or —C(═O)—, provided that a case where the aliphatic groupincludes two or more contiguous —O— or —S— is excluded, R² is a hydrogenatom or an alkyl group having 1 to 6 carbon atoms,Z¹ and Z² are independently an alkenyl group having 2 to 10 carbon atomsthat is substituted with a halogen atom, or unsubstituted,A¹ is a substituted or unsubstituted tetravalent aromatic group having 4to 30 carbon atoms,A² and A³ are independently a substituted or unsubstituted divalentalicyclic hydrocarbon group having 3 to 30 carbon atoms,A⁴ and A⁵ are independently a substituted or unsubstituted divalentaromatic group having 4 to 30 carbon atoms,A^(x1) and A^(x2) are independently an organic group having 2 to 30carbon atoms that includes at least one ring selected from the groupconsisting of a hydrocarbon ring and a heterocyclic ring,A^(y1) and A^(y2) are independently a hydrogen atom, a substituted orunsubstituted alkyl group having 1 to 6 carbon atoms, or an organicgroup having 2 to 30 carbon atoms that includes at least one ringselected from the group consisting of a hydrocarbon ring and aheterocyclic ring,provided that the ring included in A^(x1), the ring included in A^(x2),the ring optionally included in A^(y1), and the ring optionally includedin A^(y2) are either substituted or unsubstituted,A^(x1) and A^(y1) are optionally bonded to each other to form a ring,and A^(x2) and A^(y2) are optionally bonded to each other to form aring,Q¹ and Q² are independently a hydrogen atom, or a substituted orunsubstituted alkyl group having 1 to 6 carbon atoms, andm and n are independently 0 or 1.(2) The polymerizable compound according to (1), wherein the ringincluded in A^(x1), the ring included in A^(x2), the ring optionallyincluded in A^(y1), and the ring optionally included in A^(y2) are anaromatic ring.(3) The polymerizable compound according to (1), wherein the totalnumber of aromatic ring π electrons included in A^(x1) and A^(y1) is 24or less, and the total number of aromatic ring π electrons included inA^(x2) and A^(y2) is 24 or less.(4) The polymerizable compound according to (1), wherein the ring thatis optionally formed by A^(x1) and A^(y1), and the ring that isoptionally formed by A^(x2) and A^(y2), are a nitrogen-containingheterocyclic ring represented by the following formula (II),

wherein R^(x) are a hydrogen atom, a halogen atom, an alkyl group having1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinylgroup having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or analkoxy group having 1 to 6 carbon atoms, provided that R^(x) are eitheridentical or different, an arbitrary C—R^(x) linkage that forms the ringis optionally substituted with N—R³ (R³ is a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms) or —O—, and the ring optionallyincludes an unsaturated bond, a is an integer from 0 to 2, and “—” isthe bonding position.(5) The polymerizable compound according to (1), wherein A¹ is asubstituted or unsubstituted tetravalent benzene ring group, or asubstituted or unsubstituted tetravalent naphthalene ring group, and A⁴and A⁵ are independently a substituted or unsubstituted phenylene group,or a substituted or unsubstituted naphthylene group.(6) The polymerizable compound according to (1), wherein Y¹ to Y⁸ areindependently a chemical single bond, —O—, —O—C(═O)—, —C(═O)—O—, or—O—C(═O)—O—.(7) The polymerizable compound according to (1), wherein Z¹ and Z² areindependently CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—.(8) The polymerizable compound according to (1), wherein G¹ and G² areindependently a substituted or unsubstituted divalent aliphatic grouphaving 1 to 12 carbon atoms that optionally includes —O—, —O—C(═O)—,—C(═O)—O—, or —C(═O)—, provided that a case where the aliphatic groupincludes two or more contiguous —O— is excluded.(9) The polymerizable compound according to (1), wherein Y¹ to Y⁸ areindependently a chemical single bond, —O—, —O—C(═O)—, —C(═O)—O—, or—O—C(═O)—O—, Z¹ to Z³ are independently CH₂═CH—, CH₂═C(CH₃)—, orCH₂═C(Cl)—, and G¹ and G² are independently a divalent alkylene grouphaving 1 to 12 carbon atoms.(10) A polymerizable composition including at least one type of thepolymerizable compound according to any one of (1) to (9).(11) A polymerizable composition including the polymerizable compoundaccording to any one of (1) to (9), and an initiator.(12) A polymer obtained by polymerizing the polymerizable compoundaccording to any one of (1) to (9), or the polymerizable compositionaccording to (10) or (11).(13) The polymer according to (12), the polymer being a liquidcrystalline polymer.(14) An optically anisotropic article including the polymer according to(13).

Advantageous Effects of the Invention

The polymerizable compound, the polymerizable composition, and thepolymer according to the aspects of the invention make it possible toinexpensively obtain an optically anisotropic article that achievesuniform conversion of polarized light over a wide wavelength band, andexhibits satisfactory performance.

Since the optically anisotropic article according to one aspect of theinvention is produced using the polymer according to one aspect of theinvention, the optically anisotropic article can be produced at lowcost, achieves uniform conversion of polarized light over a widewavelength band, and exhibits satisfactory performance.

For example, an antireflective film may be produced by combining thefilm-shaped optically anisotropic article according to one aspect of theinvention with a polarizer. The antireflective film may suitably be usedto prevent reflection from a touch panel, an organic electroluminescentdevice, and the like.

DESCRIPTION OF EMBODIMENTS

A polymerizable compound, a polymerizable composition, a polymer, and anoptically anisotropic article according to several exemplary embodimentsof the invention are described in detail below.

1) Polymerizable Compound

A polymerizable compound according to one embodiment of the invention isa compound represented by the formula (I).

Y¹ to Y⁸ in the formula (1) are independently a chemical single bond,—O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—,—O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—.

R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R¹include a methyl group, an ethyl group, an n-propyl group, an isopropylgroup, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentylgroup, an n-hexyl group, and the like.

R¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbonatoms.

It is preferable that Y¹ to Y⁸ be independently a chemical single bond,—O—, —O—C(═O)—, —C(═O)—O—, or —O—C(═O)—O—.

G¹ and G² are independently a substituted or unsubstituted divalentaliphatic group having 1 to 20 carbon atoms.

Examples of the divalent aliphatic group having 1 to 20 carbon atomsinclude a divalent aliphatic group having a linear structure; a divalentaliphatic group having an alicyclic structure such as a saturated cyclichydrocarbon (cycloalkane) structure or an unsaturated cyclic hydrocarbon(cycloolefin) structure; and the like.

Examples of a substituent that may substitute the divalent aliphaticgroup represented by G¹ and G² include a halogen atom such as a fluorineatom, a chlorine atom, a bromine atom, and an iodine atom; an alkoxygroup having 1 to 6 carbon atoms, such as a methoxy group, an ethoxygroup, an n-propoxy group, an isopropoxy group, an n-butoxy group, asec-butoxy group, a t-butoxy group, an n-pentyloxy group, and ann-hexyloxy group; and the like. Among these, a fluorine atom, a methoxygroup, and an ethoxy group are preferable.

The aliphatic group optionally includes —O—, —S—, —O—C(═O)—, —C(═O)—O—,—O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or —C(═O)— (provided thata case where the aliphatic group includes two or more contiguous —O— or—S— is excluded). R² is a hydrogen atom, or an alkyl group having 1 to 6carbon atoms similar to that represented by R¹, and is preferably ahydrogen atom or a methyl group.

—O—, —O—C(═O)—, —C(═O)—O—, and —C(═O)— are preferable as the group thatis optionally included in the aliphatic group.

Specific examples of the aliphatic group that includes the above groupinclude —CH₂—CH₂—O—CH₂—CH₂—, —CH₂—CH₂—S—CH₂—CH₂—,—CH₂—CH₂—O—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—C(═O)—O—CH₂—, —CH₂—O—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—NR²—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—NR²—CH₂—, —CH₂—NR²—CH₂—CH₂—,—CH₂—C(═O)—CH₂—, and the like.

It is preferable that G¹ and G² be independently a divalent aliphaticgroup having a linear structure (e.g., an alkylene group having 1 to 20carbon atoms or an alkenylene group having 2 to 20 carbon atoms), morepreferably an alkylene group having 1 to 12 carbon atoms (e.g.,methylene group, ethylene group, trimethylene group, propylene group,tetramethylene group, pentamethylene group, hexamethylene group, oroctamethylene group), and particularly preferably a tetramethylene group(—(CH₂)₄—) or a hexamethylene group (—(CH₂)₆—), in order to ensure thatthe intended effects of the invention can be more advantageouslyachieved.

Z¹ and Z² are independently an alkenyl group having 2 to 10 carbon atomsthat is substituted with a halogen atom, or unsubstituted.

The number of carbon atoms of the alkenyl group is preferably 2 to 6.Examples of the halogen atom that may substitute the alkenyl grouprepresented by Z¹ and Z² include a fluorine atom, a chlorine atom, abromine atom, and the like. Among these, a chlorine atom is preferable.

Specific examples of the alkenyl group having 2 to 10 carbon atomsrepresented by Z¹ and Z² include CH₂═CH—, CH₂═C(CH₃)—, CH₂═CH—CH₂—,CH₃—CH═CH—, CH₂═CH—CH₂—CH₂—, CH₂═C(CH₃)—CH₂—CH₂—, (CH₃)₂C═CH—CH₂—,(CH₃)₂C═CH—CH₂—CH₂—, CH₂═C(Cl)—, CH₂═C(CH₃)—CH₂—, CH₃—CH═CH—CH₂—, andthe like.

It is preferable that Z¹ and Z² be independently CH₂═CH—, CH₂═C(CH₃)—,CH₂═C(Cl)—, CH₂═CH—CH₂—, CH₂═C(CH₃)—CH₂—, or CH₂═C(CH₃)—CH₂—CH₂—, morepreferably CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—, and still morepreferably CH₂═CH—, in order to more advantageously achieve the intendedeffects of the invention.

A^(x1) and A^(x2) are an organic group having 2 to 30 carbon atoms thatincludes at least one ring selected from the group consisting of ahydrocarbon ring and a heterocyclic ring.

The organic group having 2 to 30 carbon atoms represented by A^(x1) andA^(x2) may include a plurality of rings, and may include a hydrocarbonring and a heterocyclic ring.

Examples of the ring included in A^(x1) and A^(x2) include a saturatedhydrocarbon ring such as a cyclohexane ring and a cycloheptane ring; asaturated heterocyclic ring such as a tetrahydrofuran ring, atetrahydrothiophene ring, a piperidine ring, and a pyrrolidine ring; anaromatic hydrocarbon ring; a heteroaromatic ring; and the like. It ispreferable that the ring included in A^(x1) and A^(x2) be an aromaticring such as an aromatic hydrocarbon ring and a heteroaromatic ring,since the advantageous effects of the invention can be more easilyachieved.

The term “aromatic ring” used herein refers to a cyclic structure thatexhibits aromaticity in a broad sense according to Huckel's rule (i.e.,a cyclic conjugated structure that includes (4n+2) π electrons, and astructure that exhibits aromaticity in which lone pairs of heteroatoms(e.g., sulfur, oxygen, or nitrogen) are involved in the a electronsystem (e.g., thiophene, furan, and benzothiazole).

Examples of the aromatic hydrocarbon ring include a benzene ring,

a naphthalene ring, an anthracene ring, and the like.

Examples of the heteroaromatic ring include a monocyclic heteroaromaticring such as a pyrrole ring, a furan ring, a thiophene ring, a pyridinering, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrazolering, an imidazole ring, an oxazole ring, and a thiazole ring; a fusedheteroaromatic ring such as a benzothiazole ring, a benzoxazole ring, aquinoline ring, a phthalazine ring, a benzimidazole ring, abenzopyrazole ring, a benzofuran ring, and a benzothiophene ring; andthe like.

Examples of a preferable organic group having 2 to 30 carbon atomsrepresented by A^(x1) and A^(x2) that includes at least one ringselected from the group consisting of a hydrocarbon ring and aheterocyclic ring include an aromatic hydrocarbon ring group; aheteroaromatic ring group; an alkyl group that includes at least onearomatic ring selected from the group consisting of an aromatichydrocarbon ring group and a heteroaromatic ring group; an alkenyl groupthat includes at least one aromatic ring selected from the groupconsisting of an aromatic hydrocarbon ring group and a heteroaromaticring group; and an alkynyl group that includes at least one aromaticring selected from the group consisting of an aromatic hydrocarbon ringgroup and a heteroaromatic ring group.

Specific examples of the organic group preferable as A^(x1) and A^(x2)are shown below. Note that A^(x1) and A^(x2) are not limited to thefollowing organic groups. “—” in the following formulas is a bond fromthe ring (hereinafter the same).

(1) Aromatic hydrocarbon ring group

(2) Heteroaromatic ring group

wherein E is NR⁴, an oxygen atom, or a sulfur atom, and R⁴ is a hydrogenatom, or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group,ethyl group, or propyl group).

wherein X, Y, and Z are independently NR⁵, an oxygen atom, a sulfuratom, —SO—, or —SO₂— (provided that a case where two or more oxygenatoms, sulfur atoms, —SO—, or —SO₂— are situated at adjacent positionsis excluded), and R⁵ is a hydrogen atom, or an alkyl group having 1 to 6carbon atoms (e.g., methyl group, ethyl group, or propyl group) similarto that represented by R⁴.(3) Alkyl group that includes at least one aromatic ring selected fromthe group consisting of an aromatic hydrocarbon ring group and aheteroaromatic ring group

(4) Alkenyl group that includes at least one aromatic ring selected fromthe group consisting of an aromatic hydrocarbon ring group and aheteroaromatic ring group

(5) Alkynyl group that includes at least one aromatic ring selected fromthe group consisting of an aromatic hydrocarbon ring group and aheteroaromatic ring group

The ring included in A^(x1) and A^(x2) is optionally substituted with asubstituent. Examples of the substituent include a halogen atom such asa fluorine atom and a chlorine atom; a cyano group; an alkyl grouphaving 1 to 6 carbon atoms, such as a methyl group, an ethyl group, anda propyl group; an alkenyl group having 2 to 6 carbon atoms, such as avinyl group and an allyl group; an alkyl halide group having 1 to 6carbon atoms, such as a trifluoromethyl group; a substituted amino groupsuch as a dimethylamino group; an alkoxy group having 1 to 6 carbonatoms, such as a methoxy group, an ethoxy group, and an isopropoxygroup; a nitro group; an aryl group such as a phenyl group and anaphthyl group; —C(═O)—R⁶; —C(═O)—OR⁶; —SO₂R⁶; and the like. Note thatR⁶ is an alkyl group having 1 to 6 carbon atoms (e.g., methyl group orethyl group), or an aryl group having 6 to 14 carbon atoms (e.g., phenylgroup).

The ring included in A^(x1) and A^(x2) may be substituted with aplurality of identical or different substituents, and two adjacentsubstituents may be bonded to each other to form a ring. The ring formedby two adjacent substituents may be either a monocyclic ring or a fusedpolycyclic ring.

Note that the number of carbon atoms (i.e., 2 to 30) of the organicgroup represented by A^(x1) and A^(x2) refers to the total number ofcarbon atoms of the organic group excluding the number of carbon atomsof a substituent. This also applies to the number of carbon atoms of theorganic group represented by A^(y1) and A^(y2).

A^(y1) and A^(y2) are a hydrogen atom, a substituted or unsubstitutedalkyl group having 1 to 6 carbon atoms, or an organic group having 2 to30 carbon atoms that includes at least one ring selected from the groupconsisting of a hydrocarbon ring and a heterocyclic ring.

Examples of the alkyl group having 1 to 6 carbon atoms represented byA^(y1) and A^(y2) (that is substituted or unsubstituted) include amethyl group, an ethyl group, an n-propyl group, an isopropyl group, ann-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, anisopentyl group, a neopentyl group, an n-hexyl group, an isohexyl group,and the like.

Examples of a substituent that may substitute the alkyl group having 1to 6 carbon atoms include a halogen atom such as a fluorine atom and achlorine atom; a cyano group; a substituted amino group such as adimethylamino group; an alkoxy group having 1 to 6 carbon atoms, such asa methoxy group, an ethoxy group, and an isopropoxy group; an alkoxygroup having 1 to 6 carbon atoms that is substituted with an alkoxygroup having 1 to 6 carbon atoms, such as a methoxymethoxy group and amethoxyethoxy group; a nitro group; an aryl group such as a phenyl groupand a naphthyl group; a cycloalkyl group having 3 to 8 carbon atoms,such as a cyclopropyl group, a cyclopentyl group, and a cyclohexylgroup; —C(═O)—R⁷; —C(═O)—OR⁷; —SO₂R⁷; a hydroxyl group; and the like.Note that R⁷ is an alkyl group having 1 to 6 carbon atoms (e.g., methylgroup or ethyl group), or an aryl group having 6 to 14 carbon atoms(e.g., phenyl group).

Examples of the organic group having 2 to 30 carbon atoms represented byA^(y1) and A^(y2) that includes at least one ring selected from thegroup consisting of a hydrocarbon ring and a heterocyclic ring, includethose mentioned above in connection with A^(x1) and A^(x2).

The groups respectively represented by the following formulas arepreferable as the organic group having 2 to 30 carbon atoms representedby A^(x1), A^(x2), A^(y1), and A^(y2) that includes at least one ringselected from the group consisting of a hydrocarbon ring and aheterocyclic ring.

wherein X is the same as defined above.

The groups respectively represented by the following formulas are morepreferable as the organic group having 2 to 30 carbon atoms representedby A^(x1), A^(x2), A^(y1) and A^(y2) that includes at least one ringselected from the group consisting of a hydrocarbon ring and aheterocyclic ring.

wherein X and Y are the same as defined above.

The groups respectively represented by the following formulas areparticularly preferable as the organic group having 2 to 30 carbon atomsrepresented by A^(x1), A^(x2), A^(y1), and A^(y2) that includes at leastone ring selected from the group consisting of a hydrocarbon ring and aheterocyclic ring.

wherein X is the same as defined above.

These groups may be substituted at an arbitrary position with asubstituent similar to those mentioned above in connection with thesubstituent that may substitute the ring included in A^(x1) and thelike.

A^(x1) and A^(y1) and/or A^(x2) and A^(Y2) are optionally bonded to eachother to form a ring. The ring that is optionally formed by A^(x1) andA^(y1) and the ring that is optionally formed by A^(x2) and A^(y2) maybe either a monocyclic ring or a fused ring.

A nitrogen-containing heterocyclic ring represented by the followingformula (II) is preferable as the ring that is optionally formed byA^(x1) and A^(y1) and the ring that is optionally formed by A^(x2) andA^(y2).

wherein R^(x) are a hydrogen atom, a halogen atom (e.g., fluorine atom,chlorine atom, or a bromine atom), an alkyl group having 1 to 6 carbonatoms (e.g., methyl group or ethyl group), a cyano group, a nitro group,an alkylsulfinyl group having 1 to 6 carbon atoms (e.g., methylsulfinylgroup or ethylsulfinyl group), an alkylsulfonyl group having 1 to 6carbon atoms (e.g., methylsulfonyl group or ethylsulfonyl group), afluoroalkyl group having 1 to 6 carbon atoms (e.g., trifluoromethylgroup or pentafluoroethyl group), or an alkoxy group having 1 to 6carbon atoms (e.g., methoxy group or ethoxy group).

Among these, a hydrogen atom and an alkyl group having 1 to 6 carbonatoms are preferable.

R^(x) are either identical or different, and adjacent R^(x) may bebonded to each other to form a ring (e.g., saturated carbon ring orunsaturated carbon ring).

An arbitrary C—R^(x) linkage that forms the ring is optionallysubstituted with N—R³ (R³ is a hydrogen atom or an alkyl group having 1to 6 carbon atoms (e.g., methyl group or ethyl group)) or —O— (providedthat a case where two or more contiguous C—R^(x) linkages aresubstituted with —O— is excluded). The ring optionally includes anunsaturated bond. When a plurality of C—R^(x) linkages are substitutedwith N—R³, a plurality of N—R³ are either identical or different.

a is an integer from 0 to 2, and “—” is the bonding position.

Specific examples of the ring represented by the formula (II) are shownbelow.

Note that the ring represented by the formula (II) and the rings shownbelow correspond to the above part in the formula (I).

wherein R^(x) and R³ are the same as defined above.

wherein X, Y, and Z are the same as defined above.

These rings may be substituted with a substituent.

Examples of the substituent include a halogen atom, a cyano group, analkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6carbon atoms, a nitro group, —C(═O)—R⁸, —C(═O)—OR⁸, —SO₂R⁴, and thelike. Note that R⁸ is an alkyl group having 1 to 6 carbon atoms (e.g.,methyl group or ethyl group), or an aryl group having 6 to 14 carbonatoms (e.g., phenyl group).

The total number of aromatic ring π electrons included in A^(x1) andA^(y1) and the total number of aromatic ring π electrons included inA^(x2) and A^(y2) are preferably 24 or less, and more preferably 6 to18, in order to ensure that the intended effects of the invention can bemore advantageously achieved.

It is preferable that A^(x1) be an aromatic group having 4 to 30 carbonatoms, and A^(y1) be a hydrogen atom, a cycloalkyl group having 3 to 8carbon atoms, or an alkyl group having 1 to 20 carbon atoms (that isoptionally substituted with a halogen atom, a cyano group, an alkoxygroup having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbonatoms that is substituted with an alkoxy group having 1 to 6 carbonatoms, or a cycloalkyl group having 3 to 8 carbon atoms), or A^(x1) andA^(y1) be bonded to each other to form the group represented by theformula (II).

It is more preferable that A^(x1) be an aromatic group having 4 to 30carbon atoms, and A^(y1) be an alkyl group having 1 to 6 carbon atoms,or A^(x1) and A^(y1) be bonded to each other to form the grouprepresented by the formula (II).

Examples of a preferable combination of A^(x2) and A^(y2) include thosementioned above in connection with A^(x1) and A^(y1).

It is preferable that A^(x1) and A^(x2) be identical with each other,and A^(y1) and A^(y2) be identical with each other.

A¹ is a substituted or unsubstituted tetravalent aromatic group having 4to 30 carbon atoms. The tetravalent aromatic group may be a tetravalentcarbocyclic aromatic group, or may be a tetravalent heterocyclicaromatic group (heteroaromatic group). It is preferable that thetetravalent aromatic group be a tetravalent carbocyclic aromatic group,more preferably a tetravalent benzene ring group or a tetravalentnaphthalene ring group, and still more preferably a tetravalent benzenering group or a tetravalent naphthalene ring group represented by aformula among the following formulas, in order to ensure that theintended effects of the invention can be more advantageously achieved.

Note that the substituents Y¹ and Y² are also included in the followingformulas so that the bonding state can be readily understood (Y¹ and Y²are the same as defined above; hereinafter the same).

A¹ is more preferably a group among the groups respectively representedby the following formulas (A11) to (A19), still more preferably a groupamong the groups respectively represented by the formulas (A11), (A13),(A15), (A17), and (A18), and particularly preferably the grouprepresented by the formula (A11).

Examples of a substituent that may substitute the tetravalent aromaticgroup having 4 to 30 carbon atoms represented by A¹ include thosementioned above in connection with the ring included in A^(x1) and thelike. It is preferable that A¹ be unsubstituted.

A² and A³ are independently a substituted or unsubstituted divalentalicyclic hydrocarbon group having 3 to 30 carbon atoms.

Examples of the divalent alicyclic hydrocarbon group having 3 to 30carbon atoms include a cycloalkanediyl group having 3 to 30 carbonatoms, a divalent fused alicyclic group having 10 to 30 carbon atoms,and the like.

Examples of the cycloalkanediyl group having 3 to 30 carbon atomsinclude

a cyclopropanediyl group; a cyclobutanediyl group such as acyclobutane-1,2-diyl group and a cyclobutane-1,3-diyl group; acyclopentanediyl group such asa cyclopentane-1,2-diyl group and a cyclopentane-1,3-diyl group; acyclohexanediyl group such as a cyclohexane-1,2-diyl group, acyclohexane-1,3-diyl group, anda cyclohexane-1,4-diyl group; a cycloheptanediyl group such as acycloheptane-1,2-diyl group, a cycloheptane-1,3-diyl group, and acycloheptane-1,4-diyl group;a cyclooctanediyl group such as a cyclooctane-1,2-diyl group, acyclooctane-1,3-diyl group, a cyclooctane-1,4-diyl group, and acyclooctane-1,5-diyl group;a cyclodecanediyl group such as a cyclodecane-1,2-diyl group, acyclodecane-1,3-diyl group, a cyclodecane-1,4-diyl group, and acyclodecane-1,5-diyl group;a cyclododecanediyl group such as a cyclododecane-1,2-diyl group,a cyclododecane-1,3-diyl group, a cyclododecane-1,4-diyl group, anda cyclododecane-1,5-diyl group; a cyclotetradecanediyl group such asa cyclotetradecane-1,2-diyl group, a cyclotetradecane-1,3-diyl group,a cyclotetradecane-1,4-diyl group, a cyclotetradecane-1,5-diyl group,anda cyclotetradecane-1,7-diyl group; a cycloeicosanediyl group such asa cycloeicosane-1,2-diyl group and a cycloeicosane-1,10-diyl group; andthe like.

Examples of the divalent fused alicyclic group having 10 to 30 carbonatoms include a decalindiyl group such as a decalin-2,5-diyl group and adecalin-2,7-diyl group; an adamantanediyl group such as anadamantane-1,2-diyl group and an adamantane-1,3-diyl group; abicyclo[2.2.1]heptanediyl group such as a bicyclo[2.2.1]heptane-2,3-diylgroup, a bicyclo[2.2.1]heptane-2,5-diyl group, and abicyclo[2.2.1]heptane-2,6-diyl group; and the like.

These divalent alicyclic hydrocarbon groups may be substituted with asubstituent at an arbitrary position. Examples of the substituentinclude those mentioned above in connection with the ring included inA^(x1) and the like.

A² and A³ are preferably a divalent alicyclic hydrocarbon group having 3to 12 carbon atoms, more preferably a cycloalkanediyl group having 3 to12 carbon atoms, still more preferably a group among the groupsrespectively represented by the following formulas (A31) to (A34), andparticularly preferably the group represented by the formula (A32).

The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms isclassified into a cis-stereoisomer and a trans-stereoisomer based on thedifference in the steric configuration of the carbon atom bonded to Y¹and Y³ (or Y² and Y⁴). For example, a cyclohexane-1,4-diyl group isclassified into a cis-isomer (A32a) and a trans-isomer (A32b) (seebelow).

The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms maybe a cis-isomer, a trans-isomer, or a mixture of a cis-isomer and atrans-isomer. Note that it is preferable that the divalent alicyclichydrocarbon group having 3 to 30 carbon atoms be a trans-isomer or acis-isomer, and more preferably a trans-isomer, since an excellentalignment capability can be obtained.

A⁴ and A⁵ are independently a substituted or unsubstituted divalentaromatic group having 4 to 30 carbon atoms.

The aromatic group represented by A⁴ and A⁵ may be a monocyclic aromaticgroup, or may be a polycyclic aromatic group.

Specific examples of A⁴ and A⁵ include, but are not limited to, thegroups respectively represented by the following formulas.

These aromatic groups (i.e., specific examples of A⁴ and A⁵) may besubstituted with a substituent at an arbitrary position. Examples of thesubstituent include a halogen atom, a cyano group, a hydroxyl group, analkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6carbon atoms, a nitro group, a —C(═O)—OR group, and the like. Note thatR is an alkyl group having 1 to 6 carbon atoms. Among these, a halogenatom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy grouphaving 1 to 6 carbon atoms are preferable as the substituent. A fluorineatom is preferable as the halogen atom. A methyl group, an ethyl group,and a propyl group are preferable as the alkyl group having 1 to 6carbon atoms. A methoxy group and an ethoxy group are preferable as thealkoxy group having 1 to 6 carbon atoms.

It is preferable that A⁴ and A⁵ be independently a substituted orunsubstituted phenylene group, or a substituted or unsubstitutednaphthylene group, more preferably a group among the groups respectivelyrepresented by the following formula (A41), (A42), and (A43) that areoptionally substituted with a substituent, and particularly preferablythe group represented by the formula (A41) that is optionallysubstituted with a substituent, in order to ensure that the intendedeffects of the invention can be more advantageously achieved.

Q¹ and Q² are independently a hydrogen atom, or a substituted orunsubstituted alkyl group having 1 to 6 carbon atoms.

Examples of the substituted or unsubstituted alkyl group having 1 to 6carbon atoms include those mentioned above in connection with A^(x1) andthe like.

Q¹ and Q² are preferably a hydrogen atom or an alkyl group having 1 to 6carbon atoms, and more preferably a hydrogen atom or a methyl group.

m and n are independently 0 or 1. It is preferable that both m and n be0.

Note that the polymerizable compound according to one embodiment of theinvention may be a stereoisomer based on the carbon-nitrogen doublebond. These stereoisomers are also intended to be included within thescope of the invention.

The polymerizable compound according to one embodiment of the inventionmay be produced as described below, for example.

(1) Production Method 1

The polymerizable compound according to one embodiment of the inventionin which A^(x1) and A^(x2) are identical with each other, and A^(y1) andA^(y2) are identical with each other, may be produced by effecting thefollowing reaction, for example.

wherein Y¹ to Y⁸, G¹, G², Z¹, Z², A^(x1), A^(y1), A¹ to A⁵, Q¹, Q², m,and n are the same as defined above.

Specifically, the polymerizable compound represented by the formula(I-1) can be produced with high selectivity in high yield by reactingthe carbonyl compound represented by the formula (4) (carbonyl compound(4)) with the hydrazine compound represented by the formula (3)(hydrazine compound (3)) in a molar ratio (carbonyl compound(4):hydrazine compound (3)) of 1:2 to 1:3.

The above reaction may be effected in the presence of an acid catalystsuch as an organic acid (e.g., (±)-10-camphorsulfonic acid orp-toluenesulfonic acid), or an inorganic acid (e.g., hydrochloric acidor sulfuric acid). The addition of the acid catalyst may reduce thereaction time, and improve the yield. The acid catalyst is normallyadded in an amount of 0.001 to 1 mol based on 1 mol of the carbonylcompound (4). The acid catalyst may be added directly, or a solutionprepared by dissolving the acid catalyst in an appropriate solvent maybe added.

A solvent used for the above reaction is not particularly limited aslong as the solvent is inert to the reaction. Examples of the solventinclude an alcohol-based solvent such as methyl alcohol, ethyl alcohol,n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,sec-butyl alcohol, and t-butyl alcohol; an ether-based solvent such asdiethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, andcyclopentyl methyl ether; an ester-based solvent such as ethyl acetate,propyl acetate, and methyl propionate; an aromatic hydrocarbon-basedsolvent such as benzene, toluene, and xylene; an aliphatichydrocarbon-based solvent such as n-pentane, n-hexane, and n-heptane; anamide-based solvent such as N,N-dimethylformamide, N-methylpyrrolidone,and hexamethylphosphoric triamide; a sulfur-containing solvent such asdimethyl sulfoxide and sulfolane; a mixed solvent of two or moresolvents among these solvents; and the like.

Among these, an alcohol-based solvent, an ether-based solvent, and amixed solvent of an alcohol-based solvent and an ether-based solvent arepreferable.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 100 g per gram of the hydrazinecompound (3).

The reaction proceeds smoothly when the reaction temperature is withinthe range from −10° C. to the boiling point of the solvent. The reactiontime is determined taking account of the reaction scale, and is normallyseveral minutes to several hours.

The hydrazine compound (3) may be produced as described below.

wherein A^(x1) and A^(y1) are the same as defined above, and X^(a) andX^(b) are independently a leaving group (e.g., halogen atom,methanesulfonyloxy group, or p-toluenesulfonyloxy group).

Specifically, the compound represented by the formula (2a) is reactedwith the hydrazine (1) in an appropriate solvent in a molar ratio(compound (2a):hydrazine (1)) of 1:1 to 1:20 (preferably 1:2 to 1:10) toobtain the corresponding hydrazine compound (3a), and the hydrazinecompound (3a) is reacted with the compound represented by the formula(2b) to obtain the hydrazine compound (3).

Hydrazine monohydrate is normally used as the hydrazine (1). Acommercially available product may be used directly as the hydrazine(1).

A solvent used for the above reaction is not particularly limited aslong as the solvent is inert to the reaction. Examples of the solventinclude an alcohol-based solvent such as methyl alcohol, ethyl alcohol,n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,sec-butyl alcohol, and t-butyl alcohol; an ether-based solvent such asdiethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, andcyclopentyl methyl ether; an aromatic hydrocarbon-based solvent such asbenzene, toluene, and xylene; an aliphatic hydrocarbon-based solventsuch as n-pentane, n-hexane, and n-heptane; an amide-based solvent suchas N,N-dimethylformamide, N-methylpyrrolidone, and hexamethylphosphorictriamide; a sulfur-containing solvent such as dimethyl sulfoxide andsulfolane; a mixed solvent of two or more solvents among these solvents;and the like.

Among these, an alcohol-based solvent, an ether-based solvent, and amixed solvent of an alcohol-based solvent and an ether-based solvent arepreferable.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 100 g per gram of hydrazine.

The reaction proceeds smoothly when the reaction temperature is withinthe range from −10° C. to the boiling point of the solvent. The reactiontime is determined taking account of the reaction scale, and is normallyseveral minutes to several hours.

The hydrazine compound (3) may also be produced by reducing thediazonium salt (5) (see below) using a known method.

wherein A^(x1) and A^(y1) are the same as defined above, and X⁻ is ananion that is a counter ion for diazonium. Examples of the anionrepresented by X⁻ include an inorganic anion such as ahexafluorophosphoric acid ion, a fluoroboric acid ion, a chloride ion,and a sulfuric acid ion; an organic anion such as apolyfluoroalkylcarboxylic acid ion, a polyfluoroalkylsulfonic acid ion,a tetraphenylboric acid ion, an aromatic carboxylic acid ion, and anaromatic sulfonic acid ion; and the like.

Examples of a reducing agent used for the above reaction include a metalsalt reducing agent.

The term “metal salt reducing agent” normally refers to a compound thatincludes a metal having a small valence, or a compound that includes ametal ion and a hydrido source (see “Yuki Gosei Jikkenhou Handbook(Handbook of Organic Synthesis Experiments)”, 1990, edited by TheSociety of Synthetic Organic Chemistry, Japan, published by Maruzen Co.,Ltd., p. 810).

Examples of the metal salt reducing agent include NaAlH₄,NaAlH_(p)(Or)_(q) (wherein p and q are independently an integer from 1to 3, provided that p+q=4, and r is an alkyl group having 1 to 6 carbonatoms), LiAlH₄, iBu₂AlH, LiBH₄, NaBH₄, SnCl₂, CrCl₂, TiCl₃, and thelike.

The reduction reaction may be effected under known reaction conditions.For example, the reduction reaction may be effected under the reactionconditions described in JP-A-2005-336103, “Shin-Jikken Kagaku Koza (NewExperimental Chemistry Course)”, 1978, Vol. 14, published by MaruzenCo., Ltd., “Jikken Kagaku Koza (Experimental Chemistry Course)”, 1992,Vol. 20, published by Maruzen Co., Ltd., or the like.

The diazonium salt (5) may be produced from aniline or the like using aknown method.

The polymerizable compound according to one embodiment of the inventionin which A^(x1) and A^(x2) differ from each other, and A^(y1) and A^(y2)differ from each other, may be produced by effecting the reactionstepwise. Specifically, the compound (3) (1 equivalent) is reacted withthe compound (4), and a compound represented by the following formula(3′) (1 equivalent) is reacted with the reaction product to obtain thetarget product.

wherein A^(x2) and A^(Y2) are the same as defined above.

The polymerizable compound according to one embodiment of the inventionin which A^(x1) and A^(y1) or A^(x2) and A^(y2) are bonded to each otherto form a ring, may be produced by utilizing a compound represented bythe following formula (3″) as the compound (3), for example.

wherein R^(x) and a are the same as defined above.

Many of the compounds represented by the formula (3″) are knowncompounds, and may be produced using a known method (seeJP-A-2005-289988, for example). A product commercially available as thecompound represented by the formula (3″) may be used after optionalpurification.

The carbonyl compound (4) may be produced by appropriately bonding andmodifying a plurality of known compounds having the desired structure byarbitrarily combining an ether linkage (—O—)-forming reaction, an esterlinkage (—C(═O)—O— or —O—C(═O)—)-forming reaction, a carbonate linkage(—O—C(═O)—O—)-forming reaction, and an amide linkage (—C(═O)NH— or—NHC(═O)—)-forming reaction.

An ether linkage may be formed as described below.

(i) A compound represented by D1-hal (wherein hal is a halogen atom;hereinafter the same) and a compound represented by D2-OMet (wherein Metis an alkali metal (mainly sodium); hereinafter the same) are mixed andcondensed (Williamson synthesis). Note that D1 and D2 are an arbitraryorganic group (hereinafter the same).(ii) A compound represented by D1-hal and a compound represented byD2-OH are mixed and condensed in the presence of a base (e.g., sodiumhydroxide or potassium hydroxide).(iii) A compound represented by D1-J (wherein J is an epoxy group) and acompound represented by D2-OH are mixed and condensed in the presence ofa base (e.g., sodium hydroxide or potassium hydroxide).(iv) A compound represented by D1-OFN (wherein OFN is a group thatincludes an unsaturated bond) and a compound represented by D2-OMet aremixed and subjected to an addition reaction in the presence of a base(e.g., sodium hydroxide or potassium hydroxide).(v) A compound represented by D1-hal and a compound represented byD2-OMet are mixed and condensed in the presence of copper or cuprouschloride (Ullmann condensation).

An ester linkage and an amide linkage may be formed as described below.

(vi) A compound represented by D1-COOH and a compound represented byD2-OH or D2-NH₂ are subjected to dehydration and condensation in thepresence of a dehydration-condensation agent (e.g.,N,N-dicyclohexylcarbodiimide).(vii) A compound represented by D1-COOH is reacted with a halogenatingagent to obtain a compound represented by D1-CO-hal, and the compoundrepresented by D1-CO-hal is reacted with a compound represented by D2-OHor D2-NH₂ in the presence of a base.(viii) A compound represented by D1-COOH is reacted with an acidanhydride to obtain a mixed acid anhydride, and the mixed acid anhydrideis reacted with a compound represented by D2-OH or D2-NH₂.(ix) A compound represented by D1-COOH and a compound represented byD2-OH or D2-NH₂ are subjected to dehydration and condensation in thepresence of an acid catalyst or a base catalyst.

More specifically, the carbonyl compound (4) in which the grouprepresented by Z²-Y⁶-G²-Y⁴-A³-Y²- is identical with the grouprepresented by Z¹-Y⁵-G¹-Y³-A²-Y¹-, and Y¹ is a group represented byY¹¹—C(═O)—O— (hereinafter referred to as “compound (4′)”), may beproduced by effecting the following reaction.

wherein Y³, Y⁵, Y⁷, G¹, Z¹, A¹, A², A⁴, Q¹, Q², and m are the same asdefined above, Y¹¹ is a group provided that Y¹¹—C(═O)—O— is Y¹, Y¹ isthe same as defined above, and L is a leaving group (e.g., hydroxylgroup, halogen atom, methanesulfonyloxy group, or p-toluenesulfonyloxygroup).

Specifically, the dihydroxy compound represented by the formula (6)(compound (6)) is reacted with the compound represented by the formula(7) (compound (7)) in a molar ratio (compound (6):compound (7)) of 1:2to 1:4 (preferably 1:2 to 1:3) to produce the target compound (4′) withhigh selectivity in high yield.

When the compound (7) is a compound (carboxylic acid) represented by theformula (7) in which L is a hydroxyl group, the target product may beobtained by effecting the reaction in the presence of adehydration-condensation agent (e.g.,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride ordicyclohexylcarbodiimide).

The dehydration-condensation agent is normally used in an amount of 1 to3 mol based on 1 mol of the compound (7).

When the compound (7) is a compound (acid halide) represented by theformula (7) in which L is a halogen atom, the target product may beobtained by effecting the reaction in the presence of a base.

Examples of the base include an organic base such as triethylamine andpyridine; and an inorganic base such as sodium hydroxide, sodiumcarbonate, and sodium hydrogen carbonate.

The base is normally used in an amount of 1 to 3 mol based on 1 mol ofthe compound (7).

When the compound (7) is a compound (mixed acid anhydride) representedby the formula (7) in which L is a methanesulfonyloxy group or ap-toluenesulfonyloxy group, the target product may be obtained in thesame manner as in the case where L is a halogen atom.

Examples of the solvent used for the above reaction include achlorine-based solvent such as chloroform and methylene chloride; anamide-based solvent such as N-methylpyrrolidone, N,N-dimethylformamide,N,N-dimethylacetamide, and hexamethylphosphoric triamide; an ether-basedsolvent such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran,tetrahydropyran, and 1,3-dioxolane; a sulfur-containing solvent such asdimethyl sulfoxide and sulfolane; an aromatic hydrocarbon-based solventsuch as benzene, toluene, and xylene; an aliphatic hydrocarbon-basedsolvent such as n-pentane, n-hexane, and n-octane; an alicyclichydrocarbon-based solvent such as cyclopentane and cyclohexane; a mixedsolvent of two or more solvents among these solvents; and the like.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 50 g per gram of the hydroxy compound(6).

Many of the compounds (7) are known compounds. The carbonyl compound (7)may be produced by appropriately bonding and modifying a plurality ofknown compounds having a desired structure by arbitrarily combining anether linkage (—O—)-forming reaction, an ester linkage (—C(═O)—O— or—O—C(═O)—)-forming reaction, a carbonate linkage (—O—C(═O)—O—)-formingreaction, and an amide linkage (—C(═O)NH— or —NHC(═O)—)-formingreaction.

Many of the compounds (6) are known compounds, and may be produced usinga known method. For example, the compound (demethylated product)represented by the formula (6) in which A¹ is a trivalent benzene ringgroup, and Q¹ and Q² are a hydrogen atom, may be produced bysequentially adding an alkyllithium (e.g., n-butyllithium) andN,N-dimethylformamide to 1,4-dimethoxybenzene in the presence of a base(e.g., N,N,N′,N′-tetramethylethylenediamine), stirring the mixture toobtain a formyl product, and reacting boron tribromide with the product.A product commercially available as the compound (6) may be used afteroptional purification.

(2) Production Method 2

The polymerizable compound according to one embodiment of the inventionin which A^(x1) and A^(x2) are identical with each other, A^(y1) andA^(y2) are identical with each other, and -Y²-A³-Y⁴-G²-Y⁶-Z² and-Y¹-A²-Y³-G¹-Y⁵-Z¹ are identical with each other (i.e., a compoundrepresented by the following formula (I-2)), may be produced byeffecting the following reaction, for example.

wherein Y³, Y⁵, Y⁷, G¹, Z¹, A^(x1), A^(y1), A¹, A², A⁴, Q¹, Q², L, Y¹¹,and m are the same as defined above.

Specifically, the hydrazide compound represented by the formula (8)(compound (8)) is reacted with the compound (7) in a molar ratio(compound (8):compound (7)) of 1:2 to 1:4 (preferably 1:2 to 1:3) toproduce the target compound (1-2) with high selectivity in high yield.

The above reaction is effected under the same conditions as thoseemployed when reacting the compound (6) and the compound (7).

The compound (8) may be produced as described below.

wherein A^(x1), A^(x2), A¹, Q¹, and Q² are the same as defined above.

Specifically, the compound (6) is reacted with the hydrazine compound(3) in a molar ratio (compound (6):compound (3)) of 1:2 to 1:4(preferably 1:2 to 1:3) to produce the target compound (8) with highselectivity in high yield.

The above reaction is effected under the same conditions as thoseemployed when reacting the carbonyl compound (4) and the hydrazinecompound (3).

When producing the polymerizable compound according to one embodiment ofthe invention in which A^(x1) and A^(x2) differ from each other, andA^(y1) and A^(y2) differ from each other, a compound represented by thefollowing formula (8′) may be reacted with the compound (7) instead ofthe compound (8).

wherein A^(x1), A^(x2), A^(y1), A^(y2), A¹, Q¹, and Q² are the same asdefined above.

The compound (8′) may be produced by reacting the compound (3) (1equivalent) with the compound (6), and reacting the compound representedby the formula (3′) (1 equivalent) with the reaction product under thesame reaction conditions.

After completion of the reaction, a post-treatment operation normallyemployed in synthetic organic chemistry is performed, optionallyfollowed by a known separation/purification means such as columnchromatography, recrystallization, or distillation to isolate the targetproduct.

The structure of the target product may be identified by measurement(e.g., NMR spectrometry, IR spectrometry, or mass spectrometry),elemental analysis, and the like.

2) Polymerizable Composition

A polymerizable composition according to one embodiment of the inventionincludes at least one type of the polymerizable compound according toone embodiment of the invention. It is preferable that the polymerizablecomposition according to one embodiment of the invention further includean initiator. The initiator is used in order to more efficientlypolymerize the polymerizable composition according to one embodiment ofthe invention.

The initiator may be appropriately selected taking account of the typeof the polymerizable group included in the polymerizable compound. Forexample, a radical initiator may be used when the polymerizable group isa radically polymerizable group. An anionic initiator may be used whenthe polymerizable group is an anionically polymerizable group. Acationic initiator may be used when the polymerizable group is acationically polymerizable group.

Examples of the radical initiator include a thermal radical generatorthat is a compound that generates active species that initiatepolymerization of the polymerizable compound upon heating, and aphoto-radical generator that is a compound that generates active speciesthat initiate polymerization of the polymerizable compound upon exposureto exposure light (e.g., visible rays, ultraviolet rays (e.g., i-line),deep ultraviolet rays, electron beams, or X-rays). It is preferable touse the photo-radical generator.

Examples of the photo-radical generator include an acetophenone-basedcompound, a biimidazole-based compound, a triazine-based compound, anO-acyloxime-based compound, an onium salt-based compound, abenzoin-based compound, a benzophenone-based compound, anα-diketone-based compound, a polynuclear quinone-based compound, axanthone-based compound, a diazo-based compound, an imidesulfonate-based compound, and the like. These compounds generate activeradicals, or an active acid, or both active radicals and an active acid,upon exposure. These photo-radical generators may be used either aloneor in combination.

Specific examples of the acetophenone-based compound include2-hydroxy-2-methyl-1-phenylpropan-1-one,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one,1-hydroxycyclohexyl phenyl ketone,2,2-dimethoxy-1,2-diphenylethan-1-one, 1,2-octanedione,2-benzyl-2-dimethylamino-4′-morpholinobutyrophenone, and the like.

Specific examples of the biimidazole-based compound include2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole,2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole,2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4-dibromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4,6-tribromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,and the like.

When using a biimidazole-based compound as a photoinitiator, it ispreferable to use a hydrogen donor in combination with thebiimidazole-based compound since sensitivity can be further improved.

The term “hydrogen donor” used herein refers to a compound that candonate a hydrogen atom to radicals generated by the biimidazole-basedcompound upon exposure. A mercaptan-based compound, an amine-basedcompound, and the like are preferable as the hydrogen donor.

Examples of the mercaptan-based compound include2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole,2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethylaminopyridine,and the like. Examples of the amine-based compound include4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone,4-diethylaminoacetophenone, 4-dimethylaminopropiophenone,ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid,4-dimethylaminobenzonitrile, and the like.

Specific examples of the triazine-based compound include atriazine-based compound that includes a halomethyl group, such as2,4,6-tris(trichloromethyl)-s-triazine,2-methyl-4,6-bis(trichloromethyl)-s-triazine,2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, and2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

Specific examples of the O-acyloxime-based compound include1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-benzoyloxime),1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyloxime),1-[4-(benzoyl)phenyl]-octane-1,2-dione-2-(O-benzoyloxime),1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime),1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime),1-(9-ethyl-6-benzoyl-9h-carbazol-3-yl)-ethanone-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime),and the like.

A commercially available product may be used directly as thephoto-radical generator. Specific examples of a commercially availableproduct that may be used as the photo-radical generator include Irgacure907, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure907, and Irgacure OXE02 (manufactured by BASF); Adekaoptomer N1919(manufactured by Adeka Corporation); and the like.

Examples of the anionic initiator include an alkyllithium compound; amonolithium salt or a monosodium salt of biphenyl, naphthalene, pyrene,and the like; a polyfunctional initiator such as a dilithium salt and atrilithium salt; and the like.

Examples of the cationic initiator include a proton acid such assulfuric acid, phosphoric acid, perchloric acid, andtrifluoromethanesulfonic acid; a Lewis acid such as boron trifluoride,aluminum chloride, titanium tetrachloride, and tin tetrachloride; anaromatic onium salt or a combination of an aromatic onium salt and areducing agent; and the like.

These initiators may be used either alone or in combination.

The initiator is normally added to the polymerizable compositionaccording to one embodiment of the invention in an amount of 0.1 to 30parts by weight, and preferably 0.5 to 10 parts by weight, based on 100parts by weight of the polymerizable compound.

It is preferable to add a surfactant to the polymerizable compositionaccording to one embodiment of the invention in order to adjust surfacetension. The surfactant is not particularly limited, but is preferably anonionic surfactant. Examples of the nonionic surfactant include anoligomer having a molecular weight of about several thousand, such asKH-40 (manufactured by AGC Seimi Chemical Co., Ltd.). The surfactant isnormally added to the polymerizable composition according to oneembodiment of the invention in an amount of 0.01 to 10 parts by weight,and preferably 0.1 to 2 parts by weight, based on 100 parts by weight ofthe polymerizable compound.

The polymerizable composition according to one embodiment of theinvention may further include an additional additive such as anadditional copolymerizable monomer, a metal, a metal complex, a dye, apigment, a fluorescent material, a phosphorescent material, a levelingagent, a thixotropic agent, a gelling agent, a polysaccharide, a UVabsorber, an IR (infrared) absorber, an antioxidant, an ion-exchangeresin, or a metal oxide (e.g., titanium oxide). Each additive isnormally added to the polymerizable composition according to oneembodiment of the invention in an amount of 0.1 to 20 parts by weightbased on 100 parts by weight of the polymerizable compound.

The polymerizable composition according to one embodiment of theinvention may be prepared by mixing and dissolving given amounts of thepolymerizable compound according to one embodiment of the invention, theinitiator, and an optional additive in an appropriate organic solvent.

Examples of the organic solvent include a ketone such as cyclopentanone,cyclohexanone, and methyl ethyl ketone; an acetate such as butyl acetateand amyl acetate; a halogenated hydrocarbon such as chloroform,dichloromethane, and dichloroethane; an ether such as 1,4-dioxane,cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and1,3-dioxolane; and the like.

The polymerizable composition thus obtained is useful as a raw materialfor producing a polymer according to one embodiment of the invention, oran optically anisotropic article according to one embodiment of theinvention (described below).

3) Polymer

A polymer according to one embodiment of the invention is (1) a polymerobtained by polymerizing the polymerizable compound according to oneembodiment of the invention, or (2) a polymer obtained by polymerizingthe polymerizable composition according to one embodiment of theinvention.

The term “polymerization” used herein refers to a chemical reaction in abroad sense including a normal polymerization reaction and acrosslinking reaction.

(1) Polymer Obtained by Polymerizing Polymerizable Compound

The polymer obtained by polymerizing the polymerizable compoundaccording to one embodiment of the invention may be a homopolymer of thepolymerizable compound according to one embodiment of the invention, acopolymer of two or more types of the polymerizable compound accordingto one embodiment of the invention, or a copolymer of the polymerizablecompound according to one embodiment of the invention and an additionalcopolymerizable monomer.

Examples of the additional copolymerizable monomer include, but are notlimited to, 4′-methoxyphenyl 4-(2-methacryloyloxyethyloxy)benzoate,biphenyl 4-(6-methacryloyloxyhexyloxy)benzoate, 4′-cyanobiphenyl4-(2-acryloyloxyethyloxy)benzoate, 4′-cyanobiphenyl4-(2-methacryloyloxyethyloxy)benzoate, 3′,4′-difluorophenyl4-(2-methacryloyloxyethyloxy)benzoate, naphthyl4-(2-methacryloyloxyethyloxy)benzoate, 4-acryloyloxy-4′-decylbiphenyl,4-acryloyloxy-4′-cyanobiphenyl,4-(2-acryloyloxyethyloxy)-4′-cyanobiphenyl,4-(2-methacryloyloxyethyloxy)-4′-methoxybiphenyl,4-(2-methacryloyloxyethyloxy)-4′-(4″-fluorobenzyloxy)-biphenyl,4-acryloyloxy-4′-propylcyclohexylphenyl,4-methacryloyl-4′-butylbicyclohexyl, 4-acryloyl-4′-amyltolan,4-acryloyl-4′-(3,4-difluorophenyl)bicyclohexyl, (4-amylphenyl)4-(2-acryloyloxyethyl)benzoate, (4-(4′-propylcyclohexyl)phenyl)4-(2-acryloyloxyethyl)benzoate, and the like.

Examples of a commercially available product that may be used as theadditional copolymerizable monomer include LC-242 (manufactured by BASF)and the like. The compounds disclosed in JP-A-2007-002208,JP-A-2009-173893, JP-A-2009-274984, JP-A-2010-030979, JP-A-2010-031223,JP-A-2011-006360, and the like may also be used as the additionalcopolymerizable monomer.

A polyfunctional monomer that includes a plurality of polymerizableunsaturated groups (e.g., acryloyl group, methacryloyl group, vinylgroup, and allyl group) may also be used as the additionalcopolymerizable monomer.

Examples of such a polyfunctional monomer include an alkanedioldiacrylate such as 1,2-butanediol diacrylate, 1,3-butanediol diacrylate,1,4-butanediol diacrylate, neopentanediol diacrylate, and 1,6-hexanedioldiacrylate, an alkanediol dimethacrylate such as 1,2-butanedioldimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanedioldimethacrylate, neopentanediol dimethacrylate, and 1,6-hexanedioldimethacrylate, a polyethylene glycol diacrylate such as ethylene glycoldiacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate,and tetraethylene glycol diacrylate, a polypropylene glycol diacrylatesuch as propylene glycol diacrylate, dipropylene glycol diacrylate,tripropylene glycol diacrylate, and tetrapropylene glycol diacrylate, apolyethylene glycol dimethacrylate such as ethylene glycoldimethacrylate, diethylene glycol dimethacrylate, triethylene glycoldimethacrylate, and tetraethylene glycol dimethacrylate, a polypropyleneglycol dimethacrylate such as propylene glycol dimethacrylate,dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate,and tetrapropylene glycol dimethacrylate, a polyethylene glycol divinylether such as ethylene glycol divinyl ether, diethylene glycol divinylether, triethylene glycol divinyl ether, and tetraethylene glycoldivinyl ether, a polyethylene glycol diallyl ether such as ethyleneglycol diallyl ether, diethylene glycol diallyl ether, triethyleneglycol diallyl ether, and tetraethylene glycol diallyl ether, bisphenolF ethoxylate diacrylate, bisphenol F ethoxylate dimethacrylate,bisphenol A ethoxylate diacrylate, bisphenol A ethoxylatedimethacrylate, trimethylolpropane triacrylate, trimethylolpropanetrimethacrylate, trimethylolpropane ethoxylate triacrylate,trimethylolpropane ethoxylate trimethacrylate, trimethylolpropanepropoxylate triacrylate, trimethylolpropane propoxylate trimethacrylate,isocyanuric acid ethoxylate triacrylate, glycerol ethoxylatetriacrylate, glycerol propoxylate triacrylate, pentaerythritolethoxylate tetraacrylate, ditrimethylolpropane ethoxylate tetraacrylate,dipentaerythritol ethoxylate hexacrylate, and the like.

The polymerizable compound according to one embodiment of the inventionmay be (co)polymerized optionally together with the additionalcopolymerizable monomer in the presence of an appropriate initiator. Theinitiator may be used in an amount similar to that of the initiatorincluded in the polymerizable composition.

When the polymer according to one embodiment of the invention is acopolymer of the polymerizable compound according to one embodiment ofthe invention and the additional copolymerizable monomer, the content ofstructural units derived from the polymerizable compound according toone embodiment of the invention is not particularly limited, but ispreferably 50 wt % or more, and more preferably 70 wt % or more, basedon the total structural units. When the content of structural unitsderived from the polymerizable compound is within the above range, apolymer that has a high glass transition temperature (Tg) and highhardness can be obtained.

The polymer (1) may be produced by (A) (co)polymerizing thepolymerizable compound optionally together with the additionalcopolymerizable monomer in an appropriate organic solvent in thepresence of an appropriate initiator, isolating the target polymer,dissolving the polymer in an appropriate organic solvent to prepare asolution, applying the solution to an appropriate substrate to obtain afilm, and drying the film, followed by optional heating, or (B) applyinga solution prepared by dissolving the polymerizable compound and aninitiator in an organic solvent optionally together with the additionalcopolymerizable monomer to a substrate using a known coating method,removing the solvent, and effecting polymerization by applying heat oractivated energy rays, for example.

Examples of the initiator include those mentioned above in connectionwith the initiator included in the polymerizable composition.

The organic solvent used for polymerization when using the method (A) isnot particularly limited as long as the organic solvent is inert.Examples of the organic solvent include an aromatic hydrocarbon such astoluene, xylene, and mesitylene; a ketone such as cyclohexanone,cyclopentanone, and methyl ethyl ketone; an acetate such as butylacetate and amyl acetate; a halogenated hydrocarbon such as chloroform,dichloromethane, and dichloroethane; an ether such as cyclopentyl methylether, tetrahydrofuran, and tetrahydropyran; and the like. Among these,it is preferable to use a compound having a boiling point of 60 to 250°C., and preferably 60 to 150° C., from the viewpoint of handlingcapability.

Examples of the organic solvent used to dissolve the polymer whenimplementing the method (A), and the organic solvent used for the method(B), include a ketone-based solvent such as acetone, methyl ethylketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; anester-based solvent such as butyl acetate and amyl acetate; ahalogenated hydrocarbon-based solvent such as dichloromethane,chloroform, and dichloroethane; an ether-based solvent such astetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane,cyclopentyl methyl ether, 1,3-dioxolane; an aprotic polar solvent suchas N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide,gamma-butyrolactone, and N-methylpyrrolidone; and the like. Among these,it is preferable to use a compound having a boiling point of 60 to 200°C. from the viewpoint of handling capability. These solvents may be usedeither alone or in combination.

A substrate formed of a known organic or inorganic material may be usedas the substrate. Examples of the organic material include apolycycloolefin (e.g., Zeonex and Zeonor (registered trademark;manufactured by Zeon Corporation); Arton (registered trademark;manufactured by JSR Corporation); and Apel (registered trademark;manufactured by Mitsui Chemicals Inc.)), polyethylene terephthalate, apolycarbonate, a polyimide, a polyamide, polymethyl methacrylate,polystyrene, polyvinyl chloride, polytetrafluoroethylene, cellulose,cellulose triacetate, polyethersulfone, and the like. Examples of theinorganic material include silicon, glass, calcite, and the like. It ispreferable to use an organic material.

The substrate may be a single-layer substrate, or may be a laminate.

The substrate is preferably a substrate that is formed of an organicmaterial, and more preferably a resin film that is formed of the organicmaterial.

The polymer solution (method (A)) or the solution subjected topolymerization (method (B)) may be applied to the substrate using aknown coating method. Examples of the coating method include a curtaincoating method, an extrusion coating method, a roll coating method, aspin coating method, a dip coating method, a bar coating method, a spraycoating method, a slide coating method, a print coating method, and thelike.

(2) Polymer Obtained by Polymerizing Polymerizable Composition

The polymer according to one embodiment of the invention can be easilyobtained by polymerizing the polymerizable composition according to oneembodiment of the invention. It is preferable to use the polymerizablecomposition that includes the initiator (particularly a photoinitiator)in order to more efficiently effect polymerization.

Specifically, it is preferable to produce the polymer according to oneembodiment of the invention using the method (B) that applies thepolymerizable composition according to one embodiment of the inventionto a substrate, and polymerizes the applied polymerizable composition.Examples of the substrate include a substrate used to produce anoptically anisotropic article (described later), and the like.

The polymerizable composition according to one embodiment of theinvention may be applied to the substrate using a known coating method(e.g., bar coating method, spin coating method, roll coating method,gravure coating method, spray coating method, die coating method, capcoating method, or dipping method). A known organic solvent may be addedto the polymerizable composition according to one embodiment of theinvention in order to improve the applicability of the polymerizablecomposition. In this case, it is preferable to remove the organicsolvent by natural drying, drying by heating, drying under reducedpressure, drying by heating under reduced pressure, or the like, afterapplying the polymerizable composition to the substrate.

The polymerizable compound according to one embodiment of the inventionor the polymerizable composition according to one embodiment of theinvention may be polymerized by applying activated energy rays, orutilizing a thermal polymerization method, for example. It is preferableto polymerize the polymerizable compound or the polymerizablecomposition by applying activated energy rays since heating isunnecessary (i.e., the reaction can be effected at room temperature). Itis preferable to apply light (e.g., ultraviolet rays) to thepolymerizable compound or the polymerizable composition since theoperation is simple.

The temperature when applying light is preferably set to 30° C. or less.The irradiance is normally 1 W/m² to 10 kW/m², and preferably 5 W/m² to2 kW/m².

A polymer obtained by polymerizing the polymerizable compound accordingto one embodiment of the invention or the polymerizable compositionaccording to one embodiment of the invention may be removed from thesubstrate, and used alone, or may be used directly as an optical filmorganic material or the like without removing the polymer from thesubstrate.

The number average molecular weight of the polymer according to oneembodiment of the invention thus obtained is preferably 500 to 500,000,and more preferably 5000 to 300,000. When the number average molecularweight of the polymer is within the above range, the resulting filmexhibits high hardness and an excellent handling capability. The numberaverage molecular weight of the polymer may be determined by gelpermeation chromatography (GPC) using monodisperse polystyrene as astandard (eluant: tetrahydrofuran).

It is considered that the polymer according to one embodiment of theinvention has a structure in which crosslinking points are uniformlypresent within the molecule, and exhibits a high crosslinking efficiencyand excellent hardness.

The polymer according to one embodiment of the invention makes itpossible to inexpensively produce an optical film that achieves uniformconversion of polarized light over a wide wavelength band, and exhibitssatisfactory performance.

4) Optically Anisotropic Article

An optically anisotropic article according to one embodiment of theinvention includes the polymer according to one embodiment of theinvention.

The optically anisotropic article according to one embodiment of theinvention may be obtained by forming an alignment film on a substrate,and forming a liquid crystal layer on the alignment film using thepolymer according to one embodiment of the invention.

The alignment film is formed on the surface of the substrate in order toachieve in-plane alignment of an organic semiconductor compound in onedirection.

The alignment film may be obtained by applying a solution (alignmentfilm composition) that includes a polymer (e.g., polyimide, polyvinylalcohol, polyester, polyallylate, polyamideimide, or polyetherimide) tothe substrate to form a film, drying the film, and subjecting the filmto a rubbing treatment in one direction, for example.

The thickness of the alignment film is preferably 0.001 to 5 μm, andmore preferably 0.001 to 1 μm.

The rubbing treatment may be performed on the alignment film or thesubstrate. The rubbing treatment may be implemented using an arbitrarymethod. For example, the alignment film may be rubbed in a givendirection using a roll around which a cloth or felt formed of syntheticfibers (e.g., nylon) or natural fibers (e.g., cotton) is wound. It ispreferable to wash the alignment film with isopropyl alcohol or the likeafter the rubbing treatment in order to remove a fine powder (foreignsubstance) formed during the rubbing treatment, and clean the surface ofthe alignment film.

The alignment film may be provided with a function of achieving in-planealignment of a cholesteric liquid crystal layer in one direction byapplying polarized UV rays to the surface of the alignment film.

The liquid crystal layer may be formed on the alignment film using thepolymer according to one embodiment of the invention by utilizing themethod described above in connection with the polymer according to oneembodiment of the invention.

Since the optically anisotropic article according to one embodiment ofthe invention is produced using the polymer according to one embodimentof the invention, the optically anisotropic article can be produced atlow cost, achieves uniform conversion of polarized light over a widewavelength band, and exhibits satisfactory performance.

Examples of the optically anisotropic article according to oneembodiment of the invention include a retardation film, an alignmentfilm for a liquid crystal display device (liquid crystal display), apolarizer, a viewing angle enhancement film, a color filter, a low-passfilter, an optical polarization prism, an optical filter, and the like.

EXAMPLES

The invention is further described below by way of examples. Note thatthe invention is not limited to the following examples.

Example 1: Synthesis of Compound 1

Step 1: Synthesis of Intermediate A

A three-necked reactor equipped with a thermometer was charged with 7.0g (50.67 mmol) of 1,4-dimethoxybenzene, 29.44 g (253.33 mmol) ofN,N,N′,N′-tetramethylethylenediamine, and 280 ml of diethyl ether undera nitrogen stream to prepare a homogeneous solution. After cooling thesolution to 0° C., 97.4 ml (253.33 mmol) of 2.6 M n-butyllithium(n-hexane solution) was added dropwise to the solution over 30 minutes.After the dropwise addition, the reaction mixture was reacted for 5hours under reflux, and then cooled to −78° C. After the addition of18.52 g (253.33 mmol) of N,N-dimethylformamide, the mixture was stirredat −78° C. for 1 hour. After the addition of 350 ml of a 3 Nhydrochloric acid aqueous solution to the reaction mixture at −78° C.,the mixture was heated to 25° C., and 300 ml of distilled water and 200ml of a saturated sodium chloride solution were added to the mixture,followed by extraction with 700 ml of chloroform. The chloroform layerwas dried over anhydrous sodium sulfate, and sodium sulfate was filteredoff. The solvent was evaporated from the filtrate under reduced pressureusing a rotary evaporator. The resulting solid was added to 100 ml oftoluene. After stirring the mixture for 5 minutes, the resultingcrystals were filtered off to obtain 6.1 g of an intermediate A asyellow crystals (yield: 62%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 10.51 (s, 2H), 7.46 (s, 2H), 3.95(s, 6H).

Step 2: Synthesis of Intermediate B

A three-necked reactor equipped with a thermometer was charged with 3.32g (17.10 mmol) of the intermediate A synthesized in the step 1 and 160ml of dichloromethane under a nitrogen stream to prepare a solution,which was cooled to −40° C. After the addition of 51.3 ml (51.29 mmol)of boron tribromide (17% dichloromethane solution) dropwise to thesolution, the mixture was stirred at −40° C. for 1 hour. The reactionmixture was then heated to 25° C., and stirred for 2 hours. 600 ml ofice water was added to the reaction mixture, followed by extractiontwice with 500 ml of ethyl acetate. The organic layer was collected, anddried over anhydrous sodium sulfate, and sodium sulfate was filteredoff. The solvent was evaporated from the filtrate under reduced pressureusing a rotary evaporator. The resulting solid was added to 100 ml oftoluene. After stirring the mixture for 5 minutes, the resultingcrystals were filtered off to obtain 2.67 g of an intermediate B asyellow crystals (yield: 94%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 10.23 (s, 2H), 9.96 (s, 2H), 7.24(s, 2H).

Step 3: Synthesis of Intermediate C

A three-necked reactor equipped with a thermometer was charged with 6.41g (21.91 mmol) of 4-(6-acryloylhex-1-yloxy)benzoic acid (manufactured byDKSH Japan K.K.) and 50 ml of tetrahydrofuran (THF) under a nitrogenstream to prepare a homogeneous solution. After the addition of 2.56 g(22.33 mmol) of methanesulfonyl chloride to the solution, the reactorwas immersed in a water bath to adjust the temperature of the reactionmixture to 20° C. 2.30 g (22.75 mmol) of triethylamine was addeddropwise to the reaction mixture over 5 minutes while maintaining thetemperature of the reaction mixture at 20 to 25° C. After removing thereactor from the water bath, the reaction mixture was stirred at 25° C.for 1.5 hours. After the addition of 0.21 g (1.69 mmol) of4-(dimethylamino)pyridine and 1.40 g (8.43 mmol) of the intermediate B,the reactor was immersed in a water bath to adjust the temperature ofthe reaction mixture to 20° C. 2.13 g (21.07 mmol) of triethylamine wasadded dropwise to the reaction mixture over 5 minutes while maintainingthe temperature of the reaction mixture at 20 to 25° C. After thedropwise addition, the mixture was stirred at 25° C. for 2 hours. Aftercompletion of the reaction, 300 ml of distilled water and 100 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 500 ml of chloroform. The organiclayer was collected, and dried over anhydrous sodium sulfate, and sodiumsulfate was filtered off. The solvent was evaporated from the filtrateunder reduced pressure using a rotary evaporator. The residue waspurified by silica gel column chromatography (chloroform:THF=9:1) toobtain 4.29 g of a compound C as a white solid (yield: 71%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 10.25 (s, 2H), 8.18 (d, 4H, J=9.0Hz), 7.91 (s, 2H), 7.01 (d, 4H, J=9.0 Hz), 6.41 (dd, 2H, J=1.5 Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.83 (dd, 2H, J=1.5 Hz, 10.5Hz), 4.19 (t, 4H, J=6.5 Hz), 4.08 (t, 4H, J=6.5 Hz), 1.82-1.91 (m, 4H),1.69-1.78 (m, 4H), 1.44-1.60 (m, 8H).

Step 4: Synthesis of Compound 1

A three-necked reactor equipped with a thermometer was charged with 1.40g (1.96 mmol) of the intermediate C synthesized in the step 3 and 50 mlof THF under a nitrogen stream to prepare a solution. After the additionof 0.40 ml (0.40 mmol) of 1 N hydrochloric acid to the solution, 0.66 g(4.02 mmol) of 1-butyl-1-phenylhydrazine was added dropwise to themixture over 10 minutes. The mixture was stirred at 25° C. for 1 hour.After the addition of 0.24 g (1.46 mmol) of 1-butyl-1-phenylhydrazine,the mixture was stirred for 2 hours. The reaction mixture wasconcentrated using a rotary evaporator, and the concentrate was purifiedby silica gel column chromatography (chloroform:THF=98:2 (volume ratio(hereinafter the same))) to obtain 1.84 g of a compound 1 as a yellowsolid (yield: 93%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.23 (d, 4H, J=9.0 Hz), 7.86 (s,2H), 7.49 (s, 2H), 7.21-7.31 (m, 8H), 7.01 (d, 4H, J=9.0 Hz), 6.89 (t,2H, J=7.0 Hz), 6.42 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.14 (dd, 2H, J=10.5Hz, 17.5 Hz), 5.83 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.20 (t, 4H, J=6.5 Hz),4.08 (t, 4H, J=6.5 Hz), 3.75 (t, 4H, J=8.0 Hz), 1.82-1.91 (m, 4H),1.70-1.79 (m, 4H), 1.44-1.61 (m, 12H), 1.09-1.20 (m, 4H), 0, 75 (t, 6H,J=7.5 Hz).

Example 2: Synthesis of Compound 2

A three-necked reactor equipped with a thermometer was charged with 5.0g (7.0 mmol) of the intermediate C synthesized in the step 3 of Example1 and 50 ml of THF under a nitrogen stream to prepare a homogeneoussolution. After the addition of 1.4 ml (1.4 mmol) of 1 N hydrochloricacid to the solution, 2.4 g (21.0 mmol) of 1-amino-4-methylpiperazinewas added dropwise to the mixture at 25° C. over 15 minutes. After thedropwise addition, the mixture was stirred at 25° C. for 5 hours. Aftercompletion of the reaction, 300 ml of distilled water and 150 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 200 ml of ethyl acetate. The organiclayer was collected, and dried over anhydrous sodium sulfate, and sodiumsulfate was filtered off. The solvent was evaporated from the filtrateunder reduced pressure using a rotary evaporator. The residue waspurified by silica gel column chromatography (toluene:THIF=1:1) toobtain 1.7 g of a compound 2 as a light yellow solid (yield: 27%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.16 (d, 4H, J=9.0 Hz), 7.68 (s,2H), 7.47 (s, 2H), 6.98 (d, 4H, J=9.0 Hz), 6.41 (dd, 2H, J=1.5 Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.83 (dd, 2H, J=1.5 Hz, 10.5Hz), 4.19 (t, 4H, J=6.5 Hz), 4.06 (t, 4H, J=6.5 Hz), 3.09 (t, 8H, J=5.0Hz), 2.50 (t, 8H, J=5.0 Hz), 2.29 (s, 6H), 1.81-1.89 (m, 4H), 1.69-1.78(m, 4H), 1.44-1.59 (m, 8H).

Example 3: Synthesis of Compound 3

A three-necked reactor equipped with a thermometer was charged with 1.0g (1.4 mmol) of the intermediate C synthesized in the step 3 of Example1, 30 ml of THF, and 3 ml of methanol under a nitrogen stream to preparea homogeneous solution. After the addition of 0.92 g (4.2 mmol) of1,1-diphenylhydrazine hydrochloride to the solution over 10 minutes, themixture was stirred at 25° C. for 1 hour, and then stirred at 40° C. for2 hours. After completion of the reaction, 150 ml of distilled water and150 ml of saturated sodium bicarbonate water were added to the reactionmixture, followed by extraction twice with 200 ml of ethyl acetate. Theorganic layer was collected, and dried over anhydrous sodium sulfate,and sodium sulfate was filtered off. The reaction mixture wasconcentrated using a rotary evaporator, and the concentrate was purifiedby silica gel column chromatography (chloroform:THF=98:2) to obtain 1.34g of a compound 3 as a yellow solid (yield: 91%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.89 (d, 4H, J=9.0 Hz), 7.85 (s,2H), 7.22-7.28 (m, 8H), 7.15 (s, 2H), 7.09 (d, 8H, J=7.5 Hz), 7.03 (t,4H, J=7.5 Hz), 6.91 (d, 4H, J=9.0 Hz), 6.42 (dd, 2H, J=1.5 Hz, 17.5 Hz),6.14 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.84 (dd, 2H, J=1.5 Hz, 10.5 Hz),4.22 (t, 4H, J=6.5 Hz), 4.10 (t, 4H, J=6.5 Hz), 1.86-1.94 (m, 4H),1.73-1.81 (m, 4H), 1.47-1.64 (m, 8H).

Reference Example 1: Synthesis of Compound A

Step 1: Synthesis of Intermediate D

A four-necked reactor equipped with a thermometer was charged with 20 g(144.8 mmol) of 2,5-dihydroxybenzaldehyde, 105.8 g (362.0 mmol) of4-(6-acryloylhex-1-yloxy)benzoic acid (manufactured by DKSH Japan K.K.),5.3 g (43.4 mmol) of 4-(dimethylamino)pyridine, and 200 ml ofN-methylpyrrolidone under a nitrogen stream to prepare a homogeneoussolution. After the addition of 83.3 g (434.4 mmol) of1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC) to thesolution, the mixture was stirred at 25° C. for 12 hours. Aftercompletion of the reaction, the reaction mixture was added to 1.5 l ofwater, followed by extraction with 500 ml of ethyl acetate. After dryingthe ethyl acetate layer over anhydrous sodium sulfate, sodium sulfatewas filtered off. Ethyl acetate was evaporated from the filtrate underreduced pressure using a rotary evaporator to obtain a light yellowsolid. The light yellow solid was purified by silica gel columnchromatography (toluene:ethyl acetate=9:1) to obtain 75 g of anintermediate D as a white solid (yield: 75.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 10.20 (s, 1H), 8.18-8.12 (m, 4H),7.78 (d, 1H, J=2.8 Hz), 7.52 (dd, 1H, J=2.8 Hz, 8.7 Hz), 7.38 (d, 1H,J=8.7 Hz), 7.00-6.96 (m, 4H), 6.40 (dd, 2H, J=1.4 Hz, 17.4 Hz), 6.12(dd, 2H, J=10.6 Hz, 17.4 Hz), 5.82 (dd, 2H, J=1.4 Hz, 10.6 Hz), 4.18 (t,4H, J=6.4 Hz), 4.08-4.04 (m, 4H), 1.88-1.81 (m, 4H), 1.76-1.69 (m, 4H),1.58-1.42 (m, 8H).

Step 2: Synthesis of Compound A

A four-necked reactor equipped with a thermometer was charged with 10.5g (15.3 mmol) of the intermediate D synthesized in the step 1, 3.0 g(18.3 mmol) of 2-hydrazinobenzothiazole, and 80 ml of THF under anitrogen stream to prepare a homogeneous solution. After the addition of18 mg (0.08 mmol) of (±)-10-camphorsulfonic acid to the solution, themixture was stirred at 25° C. for 3 hours. After completion of thereaction, the reaction mixture was added to 800 ml of 10% sodiumbicarbonate water, followed by extraction twice with 100 ml of ethylacetate. The ethyl acetate layer was collected, and dried over anhydroussodium sulfate, and sodium sulfate was filtered off. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a light yellow solid. The light yellow solid waspurified by silica gel column chromatography (toluene:ethyl acetate=8:2)to obtain 8.0 g of a compound A as a light yellow solid (yield: 62.7%).

The structure of the target product was identified by ¹H-NMR and massspectroscopy.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.30 (br, 1H), 8.19 (s, 1H),8.17-8.12 (m, 4H), 7.76 (d, 1H, J=3.0 Hz), 7.68 (d, 1H, J=7.5 Hz),7.45-7.39 (m, 3H), 7.28 (t, 1H, J=8.0 Hz), 7.18-7.14 (m, 4H), 7.09 (t,1H, J=8.0 Hz), 6.33 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.18 (dd, 2H, J=10.5Hz, 17.5 Hz), 5.944 (dd, 1H, J=1.5 Hz, 10.5 Hz), 5.941 (dd, 1H, J=1.5Hz, 10.5 Hz), 4.14-4.10 (m, 8H), 1.80-1.75 (m, 4H), 1.69-1.63 (m, 4H),1.53-1.38 (m, 8H).

LCMS (APCI): calcd for C₄₆H₄₇N₃O₁₀S: 833[M⁺]; Found: 833.

The phase transition temperature was measured as described below usingthe compounds 1 to 3 obtained in Examples 1 to 3, the compound 1r ofReference Example 1 that was used in Comparative Example 1 (“K35”manufactured by Zeon Corporation), and the compound 2r of ReferenceExample 2 that was used in Comparative Example 2 (“LC242” manufacturedby BASF).

Measurement of Phase Transition Temperature

10 mg of each compound (compounds 1 to 3, compound 1r, and compound 2r)was weighed, and placed in a solid state between two glass substratesprovided with a polyimide alignment film subjected to a rubbingtreatment. The substrates were placed on a hot plate, heated from 40° C.to 200° C., and cooled to 40° C. A change in structure during a changein temperature was observed using a polarizing optical microscope(“ECLIPSE LV100POL” manufactured by Nikon Corporation).

The phase transition temperature measurement results are shown inTable 1. In Table 1, “C” refers to “crystal”, “N” refers to “nematic”,and “I” refers to “isotropic”. The term “crystal” means that the testcompound was in a solid phase, the term “nematic” means that the testcompound was in a nematic liquid crystal phase, and the term “isotropic”means that the test compound was in an isotropic liquid phase.

TABLE 1 Compound Phase transition temperature Example 1 Compound 1

Example 2 Compound 2

Example 3 Compound 3

Reference Example 1 Compound 1r

Reference Example 2 Compound 2r

Example 4

0.5 g of the compound 1 obtained in Example 1, 2.0 g of the compound Aobtained in Synthesis Example 1, 75 mg of Adekaoptomer N-1919(manufactured by Adeka Corporation (hereinafter the same))(photoinitiator), and 250 mg of a 1% cyclopentanone solution of KH-40(manufactured by AGC Seimi Chemical Co., Ltd. (hereinafter the same))(surfactant) were dissolved in 2.1 g of cyclopentanone and 7.65 g ofchloroform. The solution was filtered through a disposable filter havinga pore size of 0.45 μm to obtain a polymerizable composition 1.

Example 5

0.34 g of the compound 2 obtained in Example 2, 0.66 g of the compound Aobtained in Synthesis Example 1, 30 mg of Adekaoptomer N-1919(photoinitiator), and 100 mg of a 1% cyclopentanone solution of KH-40(surfactant) were dissolved in 2.2 g of cyclopentanone. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 2.

Example 6

0.5 g of the compound 3 obtained in Example 3, 0.5 g of the compound Aobtained in Synthesis Example 1, 30 mg of Adekaoptomer N-1919(photoinitiator), and 100 mg of a 1% cyclopentanone solution of KH-40(surfactant) were dissolved in 3.85 g of chloroform. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 3.

Example 7

0.34 g of the compound 3 obtained in Example 3, 0.66 g of the compound Aobtained in Synthesis Example 1, 30 mg of Adekaoptomer N-1919(photoinitiator), and 100 mg of a 1% cyclopentanone solution of KH-40(surfactant) were dissolved in 3.85 g of chloroform. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 4.

Comparative Examples 1 and 2

1.0 g of the compound 1r or 2r, 30 mg of Adekaoptomer N-1919(photoinitiator), and 100 mg of a 1% cyclopentanone solution of KH-40(surfactant) were dissolved in 2.3 g of cyclopentanone. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 1r or 2r, respectively.

Measurement of Retardation and Evaluation of Wavelength Dispersion (i)Formation of Liquid Crystal Layer Using Polymerizable Composition

Each polymerizable composition (polymerizable compositions 1 to 4, 1r,and 2r) was applied to a transparent glass substrate provided with apolyimide alignment film subjected to a rubbing treatment (manufacturedby E.H.C. Co., Ltd.) using a #4 wire bar. The resulting film was driedfor 30 seconds at the temperature shown in Table 2, and subjected to analignment treatment for 1 minute at the temperature shown in Table 2 toform a liquid crystal layer. Ultraviolet rays were applied to the liquidcrystal layer at a dose of 2000 mJ/cm² to effect polymerization toprepare a wavelength dispersion measurement sample.

(ii) Measurement of Retardation

The retardation between 400 nm and 800 nm was measured using the sampleutilizing an ellipsometer (“M2000U” manufactured by J. A. Woollam).

(iii) Evaluation of Wavelength Dispersion

The wavelength dispersion was evaluated from the values α and β thatwere calculated by the following expressions using the measuredretardation.

α=(retardation at 449.9 nm)/(retardation at 548.5 nm)

β=(retardation at 650.2 nm)/(retardation at 548.5 nm)

The value α is smaller than 1, and the value β is larger than 1 whenideal wideband wavelength dispersion (reverse wavelength dispersion) isachieved. The values α and β are almost identical when flat wavelengthdispersion is achieved. The value α is larger than 1, and the value β issmaller than 1 when normal dispersion is achieved.

Table 2 shows the thickness (μm) of the liquid crystal polymer filmsobtained by polymerizing the polymerizable compositions, the retardation(Re) at a wavelength of 548.5 nm, and the values α and β.

Note that “Ratio (%)” in Table 2 refers to the ratio (mass %) of theamount of the polymerizable compound.

TABLE 2 Polymerizable Polymerizable Drying Alignment Re Polymerizablecompound 1 compound 2 temperature temperature Thickness (548.5composition Compound Ratio (%) Compound Ratio (%) (° C.) (° C.) (μm) nm)α β Example 4 1 1 20 A 80 160 23 1.435 100.57 0.303 1.063 Example 5 2 234 A 66 120 23 1.358 124.37 0.949 1.005 Example 6 3 3 50 A 50 140 231.874 93.01 0.158 1.100 Example 7 4 3 34 A 66 140 23 1.870 124.50 0.2701.072 Comparative  1r  1r 100 — — 90 23 1.509 355.97 1.193 0.918 Example1 Comparative  2r  2r 100 — — 80 23 1.479 222.9 1.086 0.970 Example 2

As shown in Table 2, the polymers obtained in Examples 4 to 7 accordingto the invention had a wavelength dispersion in which the value α wassmaller than 1, and the value β was larger than 1.

1. A compound represented by a formula (4):

wherein Y¹ to Y⁸ are independently a chemical single bond, —O—, —S—,—O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—,—O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, R¹is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, G¹ andG² are independently a substituted or unsubstituted divalent aliphaticgroup having 1 to 20 carbon atoms that optionally includes —O—, —S—,—O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or—C(═O)—, provided that a case where the aliphatic group includes two ormore contiguous —O— or —S— is excluded, R² is a hydrogen atom or analkyl group having 1 to 6 carbon atoms, Z¹ and Z² are independently analkenyl group having 2 to 10 carbon atoms that is substituted with ahalogen atom, or unsubstituted, A¹ is a substituted or unsubstitutedtetravalent aromatic group having 4 to 30 carbon atoms, A² and A³ areindependently a substituted or unsubstituted divalent alicyclichydrocarbon group having 3 to 30 carbon atoms, A⁴ and A⁵ areindependently a substituted or unsubstituted divalent aromatic grouphaving 4 to 30 carbon atoms, Q¹ and Q² are independently a hydrogenatom, or a substituted or unsubstituted alkyl group having 1 to 6 carbonatoms, and m and n are independently 0 or
 1. 2. The compound accordingto claim 1, wherein A¹ is a substituted or unsubstituted tetravalentbenzene ring group, or a substituted or unsubstituted tetravalentnaphthalene ring group, and A⁴ and A⁵ are independently a substituted orunsubstituted phenylene group, or a substituted or unsubstitutednaphthylene group.
 3. The compound according to claim 1, wherein Y¹ toY⁸ are independently a chemical single bond, —O—, —O—C(═O)—, —C(═O)—O—,or —O—C(═O)—O—.
 4. The compound according to claim 1, wherein Z¹ and Z²are independently CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—.
 5. The compoundaccording to claim 1, wherein G¹ and G² are independently a substitutedor unsubstituted divalent aliphatic group having 1 to 12 carbon atomsthat optionally includes —O—, —O—C(═O)—, —C(═O)—O—, or —C(═O)—, providedthat a case where the aliphatic group includes two or more contiguous—O— is excluded.
 6. The compound according to claim 1, wherein Y¹ to Y⁸are independently a chemical single bond, —O—, —O—C(═O)—, —C(═O)—O—, or—O—C(═O)—O—, Z¹ and Z² are independently CH═CH—, CH₂═C(CH₃)—, orCH₂═C(Cl)—, and G¹ and G² are independently a divalent alkylene grouphaving 1 to 12 carbon atoms.
 7. A compound represented by a formula(8′):

wherein A¹ is a substituted or unsubstituted tetravalent aromatic grouphaving 4 to 30 carbon atoms, A^(x1) and A^(x2) are independently anorganic group having 2 to 30 carbon atoms that includes at least onering selected from a group consisting of a hydrocarbon ring and aheterocyclic ring, A^(y1) and A^(y2) are independently a hydrogen atom,a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,or an organic group having 2 to 30 carbon atoms that includes at leastone ring selected from a group consisting of a hydrocarbon ring and aheterocyclic ring, provided that the ring included in A^(x1), the ringincluded in A^(x2), the ring optionally included in A^(y1), and the ringoptionally included in A^(y2) are either substituted or unsubstituted,A^(x1) and A^(y1) are optionally bonded to each other to form a ring,and A^(x2) and A^(y2) are optionally bonded to each other to form aring, and Q¹ and Q² are independently a hydrogen atom, or a substitutedor unsubstituted alkyl group having 1 to 6 carbon atoms.
 8. The compoundaccording to claim 7, wherein the ring included in A^(x1), the ringincluded in A^(x2), the ring optionally included in A^(y1), and the ringoptionally included in A^(y2) are an aromatic ring.
 9. The compoundaccording to claim 7, wherein a total number of aromatic ring πelectrons included in A^(x1) and A^(y1) is 24 or less, and a totalnumber of aromatic ring π electrons included in A^(x2) and A^(y2) is 24or less.
 10. The compound according to claim 7, wherein the ring that isoptionally formed by A^(x1) and A^(y1), and the ring that is optionallyformed by A^(x2) and A^(y2), are a nitrogen-containing heterocyclic ringrepresented by a formula (II),

wherein R^(x) are a hydrogen atom, a halogen atom, an alkyl group having1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinylgroup having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or analkoxy group having 1 to 6 carbon atoms, provided that R^(x) are eitheridentical or different, an arbitrary C—R^(x) linkage that forms the ringis optionally substituted with N—R³ (R³ is a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms) or —O—, and the ring optionallyincludes an unsaturated bond, a is an integer from 0 to 2, and “—” is abonding position.
 11. The compound according to claim 7, wherein A¹ is asubstituted or unsubstituted tetravalent benzene ring group, or asubstituted or unsubstituted tetravalent naphthalene ring group.